DSC and morphological studies on the crystallization behavior of β-nucleated isotactic polypropylene composites filled with Kevlar fibers

The crystallization behavior of β-nucleated isotactic polypropylene (PP) composites filled with Kevlar fibers (KFs), as well as that of non-nucleated PP/KF composites for comparison, was investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The morphological observations revealed that the KF addition could induce thick α-transcrystalline layer around their surfaces in PP/KF composites, while no obvious transcrystalline layer could be detected in β-nucleated PP/KF composites. Detailed DSC investigations suggested that for the PP/KF composites, the dominant modification was α-form, and the crystallization process of matrix was promoted by KF addition, as illustrated by faster isothermal crystallization rate, shorter induction time, and higher crystallization temperature. However, for β-nucleated PP/KF composites, the main modification was β-form, and their crystallization characteristics were independent of KF addition, indicating that the α-nucleating effect of KFs was absent in this system. The DSC results were confirmed by further rheological and wide angle X-ray diffraction (WAXD) studies. The mechanism of the formation of transcrystalline layer was also discussed.     

Non-isothermal crystallization and crystalline structure Of PP/POE blends

Polypropylene (PP) /ethylene-octene copolymer (POE) blends with different content of POE were prepared by mixing chamber of a Haake torque rheometer. The crystallization behaviors and crystal structure of PP/POE blends were systematically investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarized optical microscopy (POM). The results showed that PP spherulites became defective and the crystallization behavior was influenced intensely with the introduction of POE. At the low content of POE, the addition of POE decreases the apparent incubation period (Δt _i) and the apparent total crystallization period (Δt _c) of PP in blends due to the heterogeneous nucleation of POE, and small amount of β-form PP crystals form because of the existence of POE. However, at high content of POE, the addition of POE decreases the mobility of PP segments due to their strong intermolecular interaction and chain entanglements, resulting in retarding the crystallization of PP, decreasing in the amount of β-form PP crystals, and increasing in Δt _i and Δt _c of PP in blends.     

β-Crystallisation tendency and structure of polypropylene grafted by maleic anhydride and its blends with isotactic polypropylene

Crystallization, melting and structure of three different commercial types of isotactic polypropylene (iPP) grafted by maleic anhydride (PP-g-MAH) with different maleic anhydride content (AC) and their β-nucleated versions were studied by X-ray diffractometry (WAXS), differential scanning calorimetry (DSC), polarised light microscopy (PLM) and scanning electron microscopy (SEM). The presence of maleic anhydride units disturbs the chain regularity, hereby decreases the crystallization tendency of iPP in general and the β-crystallisation ability in particular. β-modification of iPP (β-iPP) forms only in β-nucleated PP-g-MAH polymers studied if the anhydride content is not larger than 0.5 mass%. The influence of AC of PP-g-MAH on the feature the spherulitic structure is demonstrated by PLM and SEM micrographs. The β-nucleated iPP/PP-g-MAH blends containing 10 mass% PP-g-MAH crystallise predominantly in β-form independently of AC of the latter. The β-nuceated blends of iPP and PP-g-MAH with lowest AC crystallise in β-form in whole concentration range. The interaction parameter between iPP and PP-g-MAH polymers calculated by Nishi-Wang equation indicate limited interaction between the components.     

Preparation,non-isothermal crystallization,and melting behavior of β-nucleated isotactic polypropylene/poly (ethylene terephthalate) blends

β-nucleated PP/PET blends were prepared using nano-CaCO₃ supported β-nucleating agent (β-NA), PP as matrix, and PET as dispersion phase. The effects of preparation methods, PET content, and melting temperature on the non-isothermal crystallization behavior and the melting characteristic and polymorphic composition of PP in the blends were investigated by differential scanning calorimeter (DSC) and wide angle X-ray diffraction (WAXD). The results indicated that the PP crystallized predominantly in β-modification in the presence of β-NA. However, efficiency of β-NA for PP crystallization decreased with addition of PET and increasing PET contents. The β-nucleation of β-NA for PP crystallization in the blends was dependant on the preparation methods. The high β-nucleation and high β-PP content were obtained for PP/PET blend prepared at the temperature of 265 °C and added the β-NA into the blend at the temperature of 180 °C. However, the addition of β-PP or β-NA into blends at 265 °C decreased the β-nucleation, and no β-PP was formed because the β-NA mainly dispersed on the PET dispersion phase or at the interface between PP and PET.     

Mechanical properties and morphological structures of short glass fiber reinforced PP/EPDM composite

The mechanical properties and crystal morphological structures of short glass fiber (SGF) reinforced dynamically photo-irradiated polypropylene (PP)/ethylene-propylene-diene terpolymer (EPDM) composites were studied by mechanical tests, wide-angle X-ray diffraction (WAXD), optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analyzer (TGA). The mechanical properties of PP/EPDM composites, especially the tensile strength were greatly strengthened by dynamically photo-irradiation and the incorporation of SGF. The results from the WAXD, SEM, DSC, and TGA measurements reveal: (i) the formation of β-type crystal of PP in the PP/EPDM/SGF composite; (ii) the fiber length in dynamically photo-irradiated PP/EPDM/SGF composites are general longer than that in corresponding unirradiated samples. The size of EPDM phase in the photo-irradiated composites reduces obviously whereas the droplet number increases; (iii) photo-irradiation improves the interface adhesion between SGF and polymer matrix; (iv) the melting and crystallization temperatures of the photo-irradiated composites are not affected greatly by increasing the SGF content; (v) the thermal analysis results show that the incorporation of SGF into PP/EPDM plays an important role for increasing its thermal stability.     

Ductile–brittle‐transition phenomenon in polypropylene/ethylene‐propylene‐diene rubber blends obtained by dynamic packing injection molding: A new understanding of the rubber‐toughening mechanism

For a more complete understanding of the toughening mechanism of polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, dynamic packing injection molding was used to control the phase morphology and rubber particle orientation in the matrix. The relative impact strength of the blends increased at low EPDM contents, and then a definite ductile–brittle (D–B) transition was observed when the EPDM content reached 25 wt %, at which point blends should fail in the ductile mode with conventional molding. Wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were used to investigate the shear‐induced crystal structure, morphology, orientation, and phase separation of the blends. WAXD results showed that the observed D–B transition took place mainly for a constant crystal structure (α form). Also, no remarkable changes in the crystallinity and melting point of PP were observed by DSC. The highly oriented and elongated rubber particles were seen via SEM at high EPDM contents. Our results suggest that Wu's criterion is no longer valid when dispersed rubber particles are elongated and oriented. The possible fracture mechanism is discussed on the basis of the stress concentration in a filler‐dispersed matrix. It can be concluded that not only the interparticle distance but also the stress fields around individual particles play an important role in polymer toughening. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2086–2097, 2002     

A correction function to determine the β-fusion heat in a mixture of α- and β-PP

Blends of known amounts of α- and β-PP crystals were prepared from pure α- and pure β-PPsamples. Their fusion behaviours were studied by differential scanning calorimetry (DSC).The fusion heats of the α- and β-crystals were approximated from the DSC curves and compared with those calculated on the basis of the compositions of the blends. A correction function was found which improved the accuracy of the respective fusion heats significantly from the DSC analysis. The correction function can be used to determine the respective fusion heats of a PP sample which contains an unknown mixture of the α- and β-crystals. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis of PP-g-PIP and Properties of PP/PP-g-PIP Binary Blends

The polypropylene-graft-polyisoprene(PP-g-PIP) copolymers with different side chain length were synthesized by the combination of solid phase graft and anionic polymerization. The copolymers were characterized by nuclear magnetic resonance spectrum(~1H-NMR), gel permeation chromatography(GPC) and differential scanning calorimetry(DSC). Five PP/PP-g-PIP blends with PP-g-PIP as a flexibilizer to toughen PP were prepared and characterized by scanning electron microscope(SEM), dynamic mechanical analysis(DMA), DSC, wide-angle X-ray diffraction(WAXD). Their morphologies, glass transition temperatures, crystallinity and mechanical properties were investigated. All the results pointed out that the covalent bonding of PP and PIP increased the compatibility and interfacial adhesion, which led to PIP well dispersed in the system and small size PIP particles in the binary blends. In addition, the toughness of PP was improved while its tensile strength slightly decreased.     

Improved surface properties of polyaniline films by blending with Pluronic polymers without the modification of the other characteristics

Films of conductive polyaniline and amphiphilic Pluronic (P105) copolymer blends were prepared by dissolving the two polymers in N-methylpyrrolidinone (NMP) followed by a slow solvent evaporation at 55 degrees C. The characteristics of both doped and undoped films were determined by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), water droplet contact angles, differential scanning calorimetry (DSC), thermal gravimetry analysis (TG), wide-angle X-ray diffraction (WAXD), and tensile strength measurements. The surface of the blends became more hydrophilic than that of the hydrophobic PANI film, but the other properties of the blends did not change appreciably for Pluronic content lower than 50 wt%. Compared to PANI films, the more hydrophilic surfaces decreased the amount of bovine serum albumin protein adsorbed. By preventing biofouling, the polyaniline-Pluronic blends can become more useful as biosensors than the polyaniline films.     

Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, ¹H NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times.     

侧链液晶离聚物对PA1010/PP共混体系的增容作用

将聚酰胺（PA1010）、聚丙烯（PP）和热致型侧链液晶离聚物（SLCI）进行熔融共混，采用FTIR，SEM，DSC，WAXD研究测定了共混物中的相互作用，用形态结构，热行为和结晶行为，系统地研究了SLCI对PA101／PP共混物的增容作用。结果表明，SLCI有效地改善了PA1010／PP共混物的形态结构，增强了PA1010与PP链间的相互作用，使PA1010／PP熔点升高，结晶度提高。     

Photopolymerization and toughening performance in polypropylene of hyperbranched polyurethane acrylate

A novel UV-curable hyperbranched polyurethane acrylate (HUA) was synthesized and found to polymerize rapidly in the presence of 5 wt.% benzophenone in N₂ under UV exposure. The photopolymerization kinetics of HUA was studied by differential photocalorimetry (DPC). Its toughening effect for polypropylene (PP) was investigated by tensile and impact tests of the UV irradiated PP/HUA blends. The morphological structures and thermal behavior were determined by polarized optical microscopy, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The obtained results demonstrate that (1) the maximum photopolymerization rate increases with raising temperature up to 140 °C, whereas decreases at above 150 °C. The activation energy of 19 kJ mol⁻¹ for the photopolymerization was obtained at below 140 °C from the Arrhenius plot, while it is negative at above 150 °C. (2) The incorporation of 5 wt.% HUA greatly improved the notched impact strength of PP matrix with a slight improvement in the tensile strength and without obvious decline in breaking elongation. These results correlate well with SEM observation. (3) During the UV irradiation of PP/HUA blends, PP can be crosslinked/grafted with the cured HUA particles, resulting in the increase of the impact strength of PP matrix. (4) The cured HUA particles in the PP/HUA blends act as heterogeneous nucleation agent for PP, which results in the decrease of spherulite size and less perfection of PP crystals.     

Synthesis of PP-<Emphasis Type="Italic">g</Emphasis>-PIP and properties of PP/PP-<Emphasis Type="Italic">g</Emphasis>-PIP binary blends

The polypropylene-graft-polyisoprene (PP-g-PIP) copolymers with different side chain length were synthesized by the combination of solid phase graft and anionic polymerization. The copolymers were characterized by nuclear magnetic resonance spectrum (¹H-NMR), gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Five PP/PP-g-PIP blends with PP-g-PIP as a flexibilizer to toughen PP were prepared and characterized by scanning electron microscope (SEM), dynamic mechanical analysis (DMA), DSC, wide-angle X-ray diffraction (WAXD). Their morphologies, glass transition temperatures, crystallinity and mechanical properties were investigated. All the results pointed out that the covalent bonding of PP and PIP increased the compatibility and interfacial adhesion, which led to PIP well dispersed in the system and small size PIP particles in the binary blends. In addition, the toughness of PP was improved while its tensile strength slightly decreased.     

Preparation and properties of POSS grafted polypropylene by reactive blending

The octavinyl polyhedral oligomeric silsesquioxane (POSS) grafted polypropylene (PP) was first prepared by reactive blending. The structure and properties of physical blending and reactive blending composites of PP/POSS were investigated by wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA). WAXD analysis shows that the POSS in the reactive blending composites has better compatibility with PP than in the physical blending composites. The β-form crystalline hence disappears even the non-reactive POSS can act as an effective β-nucleating agents. DSC analysis shows the reactive blending composites have higher crystalline temperature while POSS in the physical blending composites have little effect on the crystalline temperature. The modulus of reactive blending composites increases in the presence of POSS, while that of the physical blending composites decreases with increasing POSS content.     

Thermomechanical characterization of PVDF and P(VDF-TrFE) blends containing corn starch and natural rubber

Films of poly(vinylidene fluoride), PVDF, and poly(vinylidene fluoride – trifluoroethylene), P(VDF-TrFE), containing corn starch and latex of natural rubber as additives were produced by compressing/annealing forming blends visioning applications as biomaterials. Therefore, considering the possible applications of these blends, a basic characterization has been carried out targeting to infer on their thermomechanical properties. The polymer films (PVDF and P(VDF-TrFE)) with different percentage of additives were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), differential scanning calorimetry (DSC), and dynamical-mechanical analysis (DMA). The compressing/annealing process allowed discarding the necessity of using the solvents to dissolve either PVDF or P(VDF-TrFE), which are usually toxic to human. The results showed that the polymers do not interact chemically with the additives with the blends showing high thermal stability and elasticity modulus at the same order of magnitude of the bone, for instance. The SEM imaged revealed that the blends present morphological structures of typical physical mixtures where each material can be identified within the blends.     

Thermal characterization of polypropylene/vermiculite composites

Vermiculite clay (VMT) was organically modified with a quaternary organic salt and added to polypropylene (PP). The compounds were prepared by melt intercalation using a twin extruder. The morphology of the composites was investigated through wide-angle X-ray diffraction (WAXD). The WAXD results suggested that exfoliation phenomena were found for the composites with modified clay. The thermal properties of the obtained composites were studied by means differential scanning calorimetry (DSC) and thermogravimetry (TG) measurements. A variation in the crystallinity of PP was found. A significant increase of the thermal stability of PP was achieved in the presence of the modified VMT.     

Nonisothermal crystallization behavior of isotactic polypropylene/ thermoplastic rubber blends

The morphology and crystallization behavior of blends of polypropylene (PP) and an ethylene-based thermoplastic elastomer (TPO) were investigated by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The SEM images showed a two-phase morphology for these blends. As TPO was partially crystalline, two distinct peaks were observed in both heating and cooling scans of DSC. The crystallization temperature of TPO in blends was higher than pure TPO. In contrast, the crystallization temperature of PP in blends was lower than pure PP. The crystallization behavior of blends was modeled by Avrami equation. It was observed that the presence of TPO accelerated the growth rate of crystals of PP in PP/TPO blends.     

Thermal properties of microcrystalline cellulose-filled PET–PTT blend polymer composites

Polymer composite materials were prepared from poly(ethylene terephthalate)–poly(trimethylene terephthalate) blends as the matrix and different microcrystalline cellulose (MCC) filler levels (0–40 wt%) using melt compounding followed by compression molding. The composites were analyzed using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The DSC results indicated that there is no consistent or significant influence of the MCC addition on the glass transition (T _g), melting (T _m), and crystallization temperature of the composites. With increasing MCC content, dynamic mechanical properties improved because of the reinforcing effect of the MCC. The tan δ peak values from the DMTA were not significantly changed as the MCC content increased. TG indicated that the onset temperature of rapid thermal degradation decreased with increasing MCC content. It was also found that the thermal stability of the composites slightly decreased as the MCC content increased.     

Thermal characterization of bacterial cellulose–phosphate composite membranes

Cellulose–phosphate composite membranes have been prepared from bacterial cellulose membranes (BC) and sodium polyphosphate solution. The structure and thermal behavior of the new composites were evaluated by X-ray diffraction (XRD), ³¹P-nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TG) and thermomechanical analysis (TMA). From XRD analyses the Iα and Iβ cellulose crystalline phases were identified together with crystalline sodium phosphate that covers the cellulose microfibrils as revealed by SEM. ³¹P NMR spectra show peaks assigned to Q⁰ and Q¹ phosphate structures to be compared to the Q² units that characterize the precursor polyphosphate. Glass transition temperature, T _g, obtained from TMA curves and thermal stability obtained from TG and DSC measurements, were observed to be dependent on the phosphate content.     

Thermal properties and phase transitions in blends of Nylon-6 with silk fibroin

The thermal and structural properties of binary blends of Nylon-6 (N6) and a chemically related biopolymer, Bombyx mori silk fibroin (SF), are reported in this work. Homopolymers and blends, in composition ratios of N6/SF ranging from 95/05 to 70/30, were investigated by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and wide angle X-ray scattering (WAXS). Silk fibroin typically degrades at temperatures just above 210°C, which occurs within the melting endotherm of N6. In TG studies, the measured mass remaining was slightly greater than expected, indicating the blends had improved thermal stability. No beta sheet crystals of SF were detected by FTIR analysis of the Amide I region. Strong interaction between N6 and SF chains was observed, possibly as a result of formation of hydrogen bonds between N6 and SF chains. DSC analysis showed that the addition of SF to N6 caused a decrease in the crystallization temperature, the melting temperature of the lowest melting crystals and the crystallinity of N6. Furthermore, the α-crystallographic phase dominates and the γ-crystallographic phase was not observed in N6/SF blends, in contrast to the homopolymer N6, which contains both phases. We suggest that the addition of SF might result in changes of the chain extension of N6, which lead to the appearance of α-rather than γ-phase crystals.